Negative potential

Arias F, Echegoyen L, WIson S R, Lu Q Y and Lu Q 1995 Methanofullerenes and methanofulleroids have different electrochemical behavior at negative potentials J. Am. Chem. Soc. 117 1422-7... 

The electrostatic potential at a point is the force acting on a unit positive charge placed at that point. The nuclei give rise to a positive (i.e. repulsive) force, whereas the electrons give rise to a negative potential. The electrostatic potential is an observable quantity that can be determined from a wavefunction using Equations (2.222) and (2.223) ... 

FIGURE 5 1 (a) The planar framework of u bonds in ethylene showing bond distances and angles (b) and (c) The p orbitals of two sp hybridized carbons overlap to produce a tt bond (d) The electrostatic potential map shows a region of high negative potential due to the tt elec trons above and below the plane of the atoms... 

Another problem is that the Nernst equation is a function of activities, not concentrations. As a result, cell potentials may show significant matrix effects. This problem is compounded when the analyte participates in additional equilibria. For example, the standard-state potential for the Fe "/Fe " redox couple is +0.767 V in 1 M 1TC104, H-0.70 V in 1 M ITCl, and -H0.53 in 10 M ITCl. The shift toward more negative potentials with an increasing concentration of ITCl is due to chloride s ability to form stronger complexes with Fe " than with Fe ". This problem can be minimized by replacing the standard-state potential with a matrix-dependent formal potential. Most tables of standard-state potentials also include a list of selected formal potentials (see Appendix 3D). 

If the initial concentration of Cu + is 1.00 X 10 M, for example, then the cathode s potential must be more negative than -1-0.105 V versus the SHE (-0.139 V versus the SCE) to achieve a quantitative reduction of Cu + to Cu. Note that at this potential H3O+ is not reduced to H2, maintaining a 100% current efficiency. Many of the published procedures for the controlled-potential coulometric analysis of Cu + call for potentials that are more negative than that shown for the reduction of H3O+ in Figure 11.21. Such potentials can be used, however, because the slow kinetics for reducing H3O+ results in a significant overpotential that shifts the potential of the H3O+/H2 redox couple to more negative potentials. 

Mixtures of trichloroacetate and dichloroacetate are analyzed by selecting an initial potential at which only the more easily reduced trichloroacetate is reduced. When its electrolysis is complete, the potential is switched to a more negative potential at which dichloroacetate is reduced. The total charge for the first electrolysis is used to determine the amount of trichloroacetate, and the difference in total charge between the first and second electrolyses gives the amount of dichloroacetate. 

Second, stripping is accomplished by scanning cathodically toward a more negative potential, reducing Hg2 back to Hg and returning the analyte to solution. 

The concentration of As(III) in water can be determined by differential pulse polarography in 1 M HCl. The initial potential is set to -0.1 V versus the SCE, and is scanned toward more negative potentials at a rate of 5 mV/s. Reduction of As(III) to As(0) occurs at a potential of approximately —0.44 V versus the SCE. The peak currents, corrected for the residual current, for a set of standard solutions are shown in the following table. 

Dissolved O2 is a problem when scanning toward more negative potentials where its reduction can lead to a significant cathodic current. In this procedure we are scanning toward more positive potentials and generating anodic currents thus, dissolved O2 is not an interferent. 

End views of the quadrupole assembly (a) showing the theoretically desired cross-section and (b) illustrating the practical system. In (b), a positive potential, +(U + Vcoscot), is applied to two opposed rods (A) and a negative potential, -(U + Vcoscot), to the other two (B). The dotted lines indicate planes of zero electric field. The dimension (r) is typically about 5 mm with rod diameters of 12 mm. The x- and y-axes are indicated, with the z-axis being perpendicular to the plane of the paper. 

These positive ions can be accelerated toward a cathode, which is held at a negative potential with respect to the filament. 

Therefore, the sample solution, which may or may not come from a liquid chromatographic column, is passed along a narrow capillary tube, the end of which is maintained at a high positive or negative potential. 

Nitriles. The electrolytic reduction of nitriles requires a high negative potential, but can lead to amines in good yields under the right conditions. This reaction occurs in acidic media according to the following equation (62). 

In plasma-based ion plating, the negative potential on the substrate surface can be generated by applying either a continuous d-c potential to an... 

In the presence of 6-iodo-l-phenyl-l-hexyne, the current increases in the cathodic (negative potential going) direction because the hexyne catalyticaHy regenerates the nickel(II) complex. The absence of the nickel(I) complex precludes an anodic wave upon reversal of the sweep direction there is nothing to reduce. If the catalytic process were slow enough it would be possible to recover the anodic wave by increasing the sweep rate to a value so fast that the reduced species (the nickel(I) complex) would be reoxidized before it could react with the hexyne. A quantitative treatment of the data, collected at several sweep rates, could then be used to calculate the rate constant for the catalytic reaction at the electrode surface. Such rate constants may be substantially different from those measured in the bulk of the solution. The chemical and electrochemical reactions involved are... 

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